US2632019A - Alkyl esters of phosphono bis beta cyanoethyl acetic acid and acetic acid nitrile - Google Patents

Alkyl esters of phosphono bis beta cyanoethyl acetic acid and acetic acid nitrile Download PDF

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US2632019A
US2632019A US218520A US21852051A US2632019A US 2632019 A US2632019 A US 2632019A US 218520 A US218520 A US 218520A US 21852051 A US21852051 A US 21852051A US 2632019 A US2632019 A US 2632019A
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Prior art keywords
acetic acid
phosphono
alkyl esters
bis
nitrile
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US218520A
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Elbert C Ladd
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Uniroyal Inc
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United States Rubber Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
    • C07F9/40—Esters thereof
    • C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl

Definitions

  • This invention relates to improvements in.
  • the present invention relates to the alkyl esters of bis(beta-cyanoethyl) phosphono acetic acid and of bis(beta-cyanoethyDacetonitrile, which can be represented by the formula in which R is alkyl, and A is -CN or -COOR. They are prepared by reacting one mole of the corresponding esters of phosphonoacetic acid or of phosphonoacetonitrile with two molecular proportions of acrylonitrile.
  • the reaction is accomplished by adding (preferably stepwise) two moles of the acrylonitrile to one mole of the organo-phosphorus compound.
  • An alkaline catalyst is usually required and may be added to the organo-phosphorus compound prior to the addition of the olefinic compound.
  • the reaction is usually exothermic and the temperature may be controlled within a convenient range (25 C.-75 C.) by controlling the rate of addition of the acrylonitrile or by cooling, as required.
  • Solvents may be used to moderate the reaction; for example, toluene, benzene, dioxane, tertiary butyl alcohol, or others which do not interfere with the reaction.
  • the reaction mixture may be heated (e. g., as high as 100 C.-150 C'.) for a time (one-half to four hours) to insure completeness of the reaction.
  • a process which comprises reacting two molecular proportions of acrylonitrile with one molecular proportion of a fully esterfied. alkyl ester of an acid selected from the class consist- 4 ing of phosphonoacetic acid, and phosphonoacetonitrile.

Description

Patented Mar. 17, 1953 ALKYLESTERS, F PHOSPHONO BIS BETA CYIANOETHYL ACETIC ACID AND ACETIG ACID NITRILE Elbert C. Ladd, Passaic, N. J assignonto .United:
States Rubber Company, New York, N. Y., a corporation .of, N ew. Jersey No Drawing. Application tim sca es Serial No. 218,520,
3 Claims.
This invention relates to improvements in.
chemicals.
More particularly, the present invention relates to the alkyl esters of bis(beta-cyanoethyl) phosphono acetic acid and of bis(beta-cyanoethyDacetonitrile, which can be represented by the formula in which R is alkyl, and A is -CN or -COOR. They are prepared by reacting one mole of the corresponding esters of phosphonoacetic acid or of phosphonoacetonitrile with two molecular proportions of acrylonitrile.
The reaction is accomplished by adding (preferably stepwise) two moles of the acrylonitrile to one mole of the organo-phosphorus compound. An alkaline catalyst is usually required and may be added to the organo-phosphorus compound prior to the addition of the olefinic compound.
The reaction is usually exothermic and the temperature may be controlled within a convenient range (25 C.-75 C.) by controlling the rate of addition of the acrylonitrile or by cooling, as required. Solvents may be used to moderate the reaction; for example, toluene, benzene, dioxane, tertiary butyl alcohol, or others which do not interfere with the reaction. After addition of the acrylonitrile is complete the reaction mixture may be heated (e. g., as high as 100 C.-150 C'.) for a time (one-half to four hours) to insure completeness of the reaction.
Products are isolated by fractional distillation EXANIPLE 1 (a) Preparation of intermediate.Eighty-three grams oftriethylphosphite and 37.75 grams of chloroacetonitrile are placedina round bottom; flask under a water-cooled reflux condenser;-
which condenser is connected to the atmosphere via a Dry Ice trap. The flask is heated at C.- C. for about four hours, during which time the reaction mixture darkens somewhat, and ethyl chloride is collected in the Dry Ice trap. Distillation of the reaction mixture yields the diethyl ester of phosphonoacetonitrile, b. 127 C.-131 C./3 mm., n 1.319.
Analysis (by Dumas) (b) Cyanoethylation of 1(a) :To a mixture of 35.4 grams (0.2 mole) of the product of 1 (a), 20 grams of tertiary butyl alcohol, and 1 cc. of a 35% solution of trimethylbenzylammonium hydroxide in methanol, was added slowly 21 grams (0.4 mole) of acrylonitrile, with stirring. The reaction is exothermic, and the temperature is maintained within the range 35 C.50 C. by adjusting the rate of addition of by coolin the reaction vessel with tap water. After the addition is complete the mixture is allowed to cool to room temperature, whereupon it solidifies to a crystalline mass. The solid is broken up, slurried twice with 100 ml. of ice water, filtered and air dried. There is thus obtained 52 g. of a white crystalline solid, the diethyl ester of bis(beta cyanoethyl)phosphonoacetonitrile, which, recrystallized from water, m. 75 C.-76 C'.
Analysis Found: N, 14.84%; P, 11.42%.
Theory: for
(C2H50) 2POC (CN) (CHzCHzCN) ztN', 14.84% P, 10.95%.
EXAMPLE 2 To a mixture of 33.6 grams (0.15 mole) of (CgH50hfiCH2COOCgH5 15 cc. of tertiary butyl alcohol and 1 cc. of 35% methanolic ammonia hydroxide, 16 grams (0.3 mole) of acrylonitrile is slowly added, with stirring, during the course of about one-half hour. The temperature of the reaction mixture is maintained within the range 40 C.-50 C. by cooling as required. After the reaction is com 3 plete, it is left standing at room temperature for three hours, then sufiicient hydrochloric acid is added to make the reaction mixture just acid to litmus. The reaction mixture is then concentrated in vacuo, to produce 43.7 grams of pale amber-colored liquid residue, the triethyl ester of bis(beta-cyanoethy1)phosphonoaceti acid.
Analysis Found: P, 9.67%; N, 8.12%. Theory for (mmohlfiowmcmcmic00m P, 9.33%; N, 8.48%. v
Having thus described my invention, what I claim-and desire to protect by Letters Patent is:
1. A process which comprises reacting two molecular proportions of acrylonitrile with one molecular proportion of a fully esterfied. alkyl ester of an acid selected from the class consist- 4 ing of phosphonoacetic acid, and phosphonoacetonitrile.
2. Trialkyl esters of phosphonobis-(betacyanoethyDacetic acid.
3. Dialkyl esters of phosphonobis-(betacyanoethyl) acetonitrile.
ELBERT c. LADD.
REFERENCES CITED The following references are of record in the file of this patent:
UNITED STATES PATENTS Number Name Date 2,503,245 Coover Apr. 11, 1950 2,557,805 Upson June 19, 1951 OTHER REFERENCES ,Nylen, Ber. Deut. Chem., vol. 59, page 1126 (1926). (Entire article, pages 1119 to 1128.)
Nature, vol. 167, issue No. 4,260, page 1035, June 1951.

Claims (1)

1. A PROCESS WHICH COMPRISES REACTING TWO MOLECULAR PROPORTIONS OF ACRYLONITRILE WITH ONE MOLECULAR PROPORTION OF A FULLY ESTERFIED ALKYL ESTER OF AN ACID SELECTED FROM THE CLASS CONSISTING OF PHOSPHONACETIC ACID, AND PHOSPHONOACETONITRILE.
US218520A 1951-03-30 1951-03-30 Alkyl esters of phosphono bis beta cyanoethyl acetic acid and acetic acid nitrile Expired - Lifetime US2632019A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4174343A (en) * 1978-05-05 1979-11-13 American Cyanamid Company Pentaerythrityl diphosphonate-ammonium polyphosphate combinations as flame retardants for olefin polymers

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2503245A (en) * 1948-09-16 1950-04-11 Eastman Kodak Co Solutions of acrylonitrile polymers
US2557805A (en) * 1949-01-18 1951-06-19 Du Pont Dialkyl vinyl phosphates and polymers

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2503245A (en) * 1948-09-16 1950-04-11 Eastman Kodak Co Solutions of acrylonitrile polymers
US2557805A (en) * 1949-01-18 1951-06-19 Du Pont Dialkyl vinyl phosphates and polymers

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4174343A (en) * 1978-05-05 1979-11-13 American Cyanamid Company Pentaerythrityl diphosphonate-ammonium polyphosphate combinations as flame retardants for olefin polymers

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